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Chapter 1 Analytical Objectives, or: What Analytical Chemists Do 1 1.1 What Is Analytical Science?, 2 1.2 Qualitative and Quantitative Analysis: What Does Each Tell Us?, 3 1.3 Getting Started: The Analytical Process, 6 1.4 Validation of a Method-You Have to Prove It Works!, 15 1.5 Analyze Versus Determine-They Are Different, 16 1.6 Some Useful Websites, 16 Chapter 2 Basic Tools and Operations of Analytical Chemistry 20 2.1 The Laboratory Notebook-Your Critical Record, 20 2.2 Laboratory Materials and Reagents, 23 2.3 The Analytical Balance-The Indispensible Tool, 23 2.4 Volumetric Glassware-Also Indispensible, 30 2.5 Preparation of Standard Base Solutions, 42 2.6 Preparation of Standard Acid Solutions, 42 2.7 Other Apparatus-Handling and Treating Samples, 43 2.8 Igniting Precipitates-Gravimetric Analysis, 48 2.9 Obtaining the Sample-Is It Solid, Liquid, or Gas?, 49 2.10 Operations of Drying and Preparing a Solution of the Analyte, 51 2.11 Laboratory Safety, 57 Chapter 3 Statistics and Data Handling in Analytical Chemistry 62 3.1 Accuracy and Precision: There Is a Difference, 62 3.2 Determinate Errors-They Are Systematic, 63 3.3 Indeterminate Errors-They Are Random, 64 3.4 Significant Figures: How Many Numbers Do You Need?, 65 3.5 Rounding Off, 71 3.6 Ways of Expressing Accuracy, 71 3.7 Standard Deviation-The Most Important Statistic, 72 3.8 Propagation of Errors-Not Just Additive, 75 3.9 Significant Figures and Propagation of Error, 81 3.10 Control Charts, 83 3.11 The Confidence Limit-How Sure Are You?, 84 3.12 Tests of Significance-Is There a Difference?, 86 3.13 Rejection of a Result: The Q Test, 95 3.14 Statistics for Small Data Sets, 98 3.15 Linear Least Squares-How to Plot the Right Straight Line, 99 3.16 Correlation Coefficient and Coefficient of Determination, 104 3.17 Detection Limits-There Is No Such Thing as Zero, 105 3.18 Statistics of Sampling-How Many Samples, How Large?, 107 3.19 Powering a Study: Power Analysis, 110 3.20 Use of Spreadsheets in Analytical Chemistry, 112 3.21 Using Spreadsheets for Plotting Calibration Curves, 117 3.22 Slope, Intercept, and Coefficient of Determination, 118 3.23 LINEST for Additional Statistics, 119 3.24 Statistics Software Packages, 120 Chapter 4 Good Laboratory Practice: Quality Assurance and Method Validation 132 4.1 What Is Good Laboratory Practice?, 133 4.2 Validation of Analytical Methods, 134 4.3 Quality Assurance-Does the Method Still Work?, 143 4.4 Laboratory Accreditation, 144 4.5 Electronic Records and Electronic Signatures: 21 CFR, Part 11, 145 4.6 Some Official Organizations, 146 Chapter 5 Stoichiometric Calculations: The Workhorse of the Analyst 149 5.1 Review of the Fundamentals, 149 5.2 How Do We Express Concentrations of Solutions?, 152 5.3 Expressions of Analytical Results-So Many Ways, 159 5.4 Volumetric Analysis: How Do We Make Stoichiometric Calculations?, 166 5.5 Volumetric Calculations-Let's Use Molarity, 169 5.6 Titer-How to Make Rapid Routine Calculations, 179 5.7 Weight Relationships-You Need These for Gravimetric Calculations, 180 Chapter 6 General Concepts of Chemical Equilibrium 188 6.1 Chemical Reactions: The Rate Concept, 188 6.2 Types of Equilibria, 190 6.3 Gibbs Free Energy and the Equilibrium Constant, 191 6.4 Le Châtelier's Principle, 192 6.5 Temperature Effects on Equilibrium Constants, 192 6.6 Pressure Effects on Equilibria, 192 6.7 Concentration Effects on Equilibria, 193 6.8 Catalysts, 193 6.9 Completeness of Reactions, 193 6.10 Equilibrium Constants for Dissociating or Combining Species-Weak Electrolytes and Precipitates, 194 6.11 Calculations Using Equilibrium Constants-Composition at Equilibrium?, 195 6.12 The Common Ion Effect-Shifting the Equilibrium, 203 6.13 Systematic Approach to Equilibrium Calculations-How to Solve Any Equilibrium Problem, 204 6.14 Some Hints for Applying the Systematic Approach for Equilibrium Calculations, 208 6.15 Heterogeneous Equilibria-Solids Don't Count, 211 6.16 Activity and Activity Coefficients-Concentration Is Not the Whole Story, 211 6.17 The Diverse Ion Effect: The Thermodynamic Equilibrium Constant and Activity Coefficients, 217 Chapter 7 Acid-Base Equilibria 222 7.1 The Early History of Acid-Base Concepts, 222 7.2 Acid-Base Theories-Not All Are Created Equal, 223 7.3 Acid-Base Equilibria in Water, 225 7.4 The pH Scale, 227 7.5 pH at Elevated Temperatures: Blood pH, 231 7.6 Weak Acids and Bases-What Is the pH?, 232 7.7 Salts of Weak Acids and Bases-They Aren't Neutral, 234 7.8 Buffers-Keeping the pH Constant (or Nearly So), 238 7.9 Polyprotic Acids and Their Salts, 245 7.10 Ladder Diagrams, 247 7.11 Fractions of Dissociating Species at a Given pH: a Values-How Much of Each Species?, 248 7.12 Salts of Polyprotic Acids-Acid, Base, or Both?, 255 7.13 Physiological Buffers-They Keep You Alive, 261 7.14 Buffers for Biological and Clinical Measurements, 263 7.15 Diverse Ion Effect on Acids and Bases: cKa and cKb-Salts Change the pH, 266 7.16 log C-pH Diagrams, 266 7.17 Exact pH Calculators, 269 Chapter 8 Acid-Base Titrations 281 8.1 Strong Acid versus Strong Base-The Easy Titrations, 282 8.2 The Charge Balance Method-An Excel Exercise for the Titration of a Strong Acid and a Strong Base, 285 8.3 Detection of the End Point: Indicators, 288 8.4 Standard Acid and Base Solutions, 290 8.5 Weak Acid versus Strong Base-A Bit Less Straightforward, 290 8.6 Weak Base versus Strong Acid, 295 8.7 Titration of Sodium Carbonate-A Diprotic Base, 296 8.8 Using a Spreadsheet to Perform the Sodium Carbonate-HCl Titration, 298 8.9 Titration of Polyprotic Acids, 300 8.10 Mixtures of Acids or Bases, 302 8.11 Equivalence Points from Derivatives of a Titration Curve, 304 8.12 Titration of Amino Acids-They Are Acids and Bases, 309 8.13 Kjeldahl Analysis: Protein Determination, 310 8.14 Titrations Without Measuring Volumes, 312 Chapter 9 Complexometric Reactions and Titrations 322 9.1 Complexes and Formation Constants-How Stable Are Complexes?, 322 9.2 Chelates: EDTA-The Ultimate Titrating Agent for Metals, 325 9.3 Metal-EDTA Titration Curves, 331 9.4 Detection of the End Point: Indicators-They Are Also Chelating Agents, 334 9.5 Other Uses of Complexes, 336 9.6 Cumulative Formation Constants ß and Concentrations of Specific Species in Stepwise Formed Complexes, 336 Chapter 10 Gravimetric Analysis and Precipitation Equilibria 342 10.1 How to Perform a Successful Gravimetric Analysis, 343 10.2 Gravimetric Calculations-How Much Analyte Is There?, 349 10.3 Examples of Gravimetric Analysis, 353 10.4 Organic Precipitates, 353 10.5 Precipitation Equilibria: The Solubility Product, 355 10.6 Diverse Ion Effect on Solubility: Ksp and Activity Coefficients, 361 Chapter 11 Precipitation Reactions and Titrations 366 11.1 Effect of Acidity on Solubility of Precipitates: Conditional Solubility Product, 366 11.2 Mass Balance Approach for Multiple Equilibria, 368 11.3 Effect of Complexation on Solubility: Conditional Solubility Product, 372 11.4 Precipitation Titrations, 374 Chapter 12 Electrochemical Cells and Electrode Potentials 383 12.1 What Are Redox Reactions?, 384 12.2 Electrochemical Cells-What Electroanalytical Chemists Use, 384 12.3 Nernst Equation-Effects of Concentrations on Potentials, 390 12.4 Formal Potential-Use It for Defined Nonstandard Solution Conditions, 394 12.5 Limitations of Electrode Potentials, 395 Chapter 13 Potentiometric Electrodes and Potentiometry 399 13.1 Metal Electrodes for Measuring the Metal Cation, 400 13.2 Metal-Metal Salt Electrodes for Measuring the Salt Anion, 401 13.3 Redox Electrodes-Inert Metals, 402 13.4 Voltaic Cells without Liquid Junction-For Maximum Accuracy, 404 13.5 Voltaic Cells with Liquid Junction-The Practical Kind, 405 13.6 Reference Electrodes: The Saturated Calomel Electrode, 407 13.7 Measurement of Potential, 409 13.8 Determination of Concentrations from Potential Measurements, 411 13.9 Residual Liquid-Junction Potential-It Should Be Minimized, 411 13.10 Accuracy of Direct Potentiometric Measurements-Voltage Error versus Activity Error, 412 13.11 Glass pH Electrode-Workhorse of Chemists, 413 13.12 Standard Buffers-Reference for pH Measurements, 418 13.13 Accuracy of pH Measurements, 420 13.14 Using the pH Meter-How Does It Work?, 421 13.15 pH Measurement of Blood-Temperature Is Important, 422 13.16 pH Measurements in Nonaqueous Solvents, 423 13.17 Ion-Selective Electrodes, 424 13.18 Chemical Analysis on Mars using Ion-Selective Electrodes, 432 Chapter 14 Redox and Potentiometric Titrations 437 14.1 First: Balance the Reduction-Oxidation Reaction, 437 14.2 Calculation of the Equilibrium Constant of a Reaction-Needed to Calculate Equivalence Point Potentials, 438 14.3 Calculating Redox Titration Curves, 441 14.4 Visual Detection of the End Point, 445 14.5 Titrations Involving Iodine: Iodimetry and Iodometry, 447 14.6 Titrations with Other Oxidizing Agents, 452 14.7 Titrations with Other Reducing Agents, 454 14.8 Preparing the Solution-Getting the Analyte in the Right Oxidation State before Titration, 454 14.9 Potentiometric Titrations (Indirect Potentiometry), 456 Chapter 15 Voltammetry and Electrochemical Sensors 466 15.1 Voltammetry, 467 15.2 Amperometric Electrodes-Measurement of Oxygen, 472 15.3 Electrochemical Sensors: Chemically Modified Electrodes, 472 15.4 Ultramicroelectrodes, 474 15.5 Microfabricated Electrochemical Sensors, 474 15.6 Micro and Ultramicroelectrode Arrays, 475 Chapter 16 Spectrochemical Methods 477 16.1 Interaction of Electromagnetic Radiation with Matter, 478 16.2 Electronic Spectra and Molecular Structure, 484 16.3 Infrared Absorption and Molecular Structure, 489 16.4 Near-Infrared Spectrometry for Nondestructive Testing, 491 16.5 Spectral Databases-Identifying Unknowns, 493 16.6 Solvents for Spectrometry, 493 16.7 Quantitative Calculations, 494 16.8 Spectrometric Instrumentation, 504 16.9 Types of Instruments, 519 16.10 Array Spectrometers-Getting the Entire Spectrum at Once, 522 16.11 Fourier Transform Infrared Spectrometers, 523 16.12 Near-IR Instruments, 525 16.13 Spectrometric Error in Measurements, 526 16.14 Deviation from Beer's Law, 527 16.15 Fluorometry, 530 16.16 Chemiluminescence, 538 16.17 Fiber-Optic Sensors, 540 Chapter 17 Atomic Spectrometric Methods 548 17.1 Principles: Distribution between Ground and Excited States-Most Atoms Are in the Ground State, 550 17.2 Flame Emission Spectrometry, 553 17.3 Atomic Absorption Spectrometry, 556 17.4 Sample Preparation-Sometimes Minimal, 567 17.5 Internal Standard and Standard Addition Calibration, 567 17.6 Atomic Emission Spectrometry: The Induction Coupled Plasma (ICP), 569 17.7 Atomic Fluorescence Spectrometry, 574 Chapter 18 Sample Preparation: Solvent and Solid-Phase Extraction 579 18.1 Distribution Coefficient, 579 18.2 Distribution Ratio, 580 18.3 Percent Extracted, 581 18.4 Solvent Extraction of Metals, 583 18.5 Accelerated and Microwave-Assisted Extraction, 585 18.6 Solid-Phase Extraction, 586 18.7 Microextraction, 590 18.8 Solid-Phase Nanoextraction (SPNE), 593 Chapter 19 Chromatography: Principles and Theory 596 19.1 Countercurrent Extraction: The Predecessor to Modern Liquid Chromatography, 598 19.2 Principles of Chromatographic Separations, 603 19.3 Classification of Chromatographic Techniques, 604 19.4 Theory of Column Efficiency in Chromatography, 607 19.5 Chromatography Simulation Software, 616 Chapter 20 Gas Chromatography 619 20.1 Performing GC Separations, 620 20.2 Gas Chromatography Columns, 623 20.3 Gas Chromatography Detectors, 630 20.4 Temperature Selection, 638 20.5 Quantitative Measurements, 639 20.6 Headspace Analysis, 641 20.7 Thermal Desorption, 641 20.8 Purging and Trapping, 642 20.9 Small and Fast, 643 20.10 Separation of Chiral Compounds, 644 20.11 Two-Dimensional GC, 645 Chapter 21 Liquid Chromatography and Electrophoresis 649 21.1 High-Performance Liquid Chromatography, 651 21.2 Stationary Phases in HPLC, 654 21.3 Equipment for HPLC, 665 21.4 Ion Chromatography, 692 21.5 HPLC Method Development, 700 21.6 UHPLC and Fast LC, 701 21.7 Open Tubular Liquid Chromatography (OTLC), 702 21.8 Thin-Layer Chromatography, 702 21.9 Electrophoresis, 708 21.10 Capillary Electrophoresis, 711 21.11 Electrophoresis Related Techniques, 724 Chapter 22 Mass Spectrometry 735 22.1 Principles of Mass Spectrometry, 735 22.2 Inlets and Ionization Sources, 740 22.3 Gas Chromatography-Mass Spectrometry, 741 22.4 Liquid Chromatography-Mass Spectrometry, 746 22.5 Laser Desorption/Ionization, 750 22.6 Secondary Ion Mass Spectrometry, 752 22.7 Inductively Coupled Plasma-Mass Spectrometry, 753 22.8 Mass Analyzers and Detectors, 753 22.9 Hybrid Instruments and Tandem Mass Spectrometry, 764 Chapter 23 Kinetic Methods of Analysis 769 23.1 Kinetics-The Basics, 769 23.2 Catalysis, 771 23.3 Enzyme Catalysis, 772 Chapter 24 Automation in Measurements 784 24.1 Principles of Automation, 784 24.2 Automated Instruments: Process Control, 785 24.3 Automatic Instruments, 787 24.4 Flow Injection Analysis, 789 24.5 Sequential Injection Analysis, 791 24.6 Laboratory Information Management Systems, 792 Clinical Chemistry C1 25.1 Composition of Blood, C1 25.2 Collection and Preservation of Samples, C3 25.3 Clinical Analysis-Common Determinations, C4 25.4 Immunoassay, C6 Chapter 26 Environmental Sampling and Analysis EN1 26.1 Getting a Meaningful Sample, EN1 26.2 Air Sample Collection and Analysis, EN2 26.3 Water Sample Collection and Analysis, EN9 26.4 Soil and Sediment Sampling, EN11 26.5 Sample Preparation for Trace Organics, EN12 26.6 Contaminated Land Sites-What Needs to Be Analyzed?, EN12 26.7 EPA Methods and Performance-Based Analyses, EN13 Century of the Gene-Genomics and Proteomics: DNA Sequencing and Protein Profiling G1 G.1 Of What Are We Made?, G1 G.2 What Is DNA?, G3 G.3 Human Genome Project, G3 G.4 How Are Genes Sequenced?, G5 G.5 Replicating DNA: The Polymerase Chain Reaction, G6 G.6 Plasmids and Bacterial Artificial Chromosomes (BACs), G7 G.7 DNA Sequencing, G8 G.8 Whole Genome Shotgun Sequencing, G11 G.9 Single-Nucleotide Polymorphisms, G11 G.10 DNA Chips, G12 G.11 Draft Genome, G13 G.12 Genomes and Proteomics: The Rest of the Story, G13 APPENDIX A LITERATURE OF ANALYTICAL CHEMISTRY 794 APPENDIX B REVIEW OF MATHEMATICAL OPERATIONS: EXPONENTS, LOGARITHMS, AND THE QUADRATIC FORMULA 797 APPENDIX C TABLES OF CONSTANTS 801 Table C.1 Dissociation Constants for Acids, 801 Table C.2a Dissociation Constants for Basic Species, 802 Table C.2b Acid Dissociation Constants for Basic Species, 803 Table C.3 Solubility Product Constants, 803 Table C.4 Formation Constants for Some EDTA Metal Chelates, 805 Table C.5 Some Standard and Formal Reduction Electrode Potentials, 806 APPENDIX D SAFETY IN THE LABORATORY S1 APPENDIX E PERIODIC TABLES ON THE WEB P1 APPENDIX F ANSWERS TO PROBLEMS 808 Experiments E1 Use of Apparatus Experiment 1 Use of the Analytical Balance, E1 Experiment 2 Use of the Pipet and Buret and Statistical Analysis, E2 Experiment 3 Analysis of Volumetric Measurements Using Spectrophotometric Microplate Readers and Spreadsheet Calculations, E4 Gravimetry Experiment 4 Gravimetric Determination of Chloride, E6 Experiment 5 Gravimetric Determination of SO3 in a Soluble Sulfate, E9 Experiment 6 Gravimetric Determination of Nickel in a Nichrome Alloy, E11 Acid-Base Titrations Experiment 7 Determination of Replaceable Hydrogen in Acid by Titration with Sodium Hydroxide, E12 Experiment 8 Determination of Total Alkalinity of Soda Ash, E14 Experiment 9 Determination of Aspirin Using Back Titration, E16 Experiment 10 Determination of Hydrogen Carbonate in Blood Using Back-Titration, E18 Complexometric Titration Experiment 11 Determination of Water Hardness with EDTA, E19 Precipitation Titrations Experiment 12 Determination of Silver in an Alloy: Volhard's Method, E21 Experiment 13 Determination of Chloride in a Soluble Chloride: Fajans' Method, E23 Potentiometric Measurements Experiment 14 Determination of the pH of Hair Shampoos, E24 Experiment 15 Potentiometric Determination of Fluoride in Drinking Water Using a Fluoride Ion-Selective Electrode, E25 Reduction-Oxidation Titrations Experiment 16 Analysis of an Iron Alloy or Ore by Titration with Potassium Dichromate, E27 Experiment 17 Analysis of Commercial Hypochlorite or Peroxide Solution by Iodometric Titration, E30 Experiment 18 Iodometric Determination of Copper, E32 Experiment 19 Determination of Antimony by Titration with Iodine, E34 Experiment 20 Microscale Quantitative Analysis of Hard-Water Samples Using an Indirect Potassium Permanganate Redox Titration, E36 Potentiometric Titrations Experiment 21 pH Titration of Unknown Soda Ash, E38 Experiment 22 Potentiometric Titration of a Mixture of Chloride and Iodide, E40 Spectrochemical Measurements Experiment 23 Spectrophotometric Determination of Iron, E41 Experiment 24 Spectrophotometric Determination of Iron in Vitamin Tablets Using a 96 Well Plate Reader, E43 Experiment 25 Determination of Nitrate Nitrogen in Water, E46 Experiment 26 Spectrophotometric Determination of Lead on Leaves Using Solvent Extraction, E47 Experiment 27 Spectrophotometric Determination of Inorganic Phosphorus in Serum, E48 Experiment 28 Spectrophotometric Determination of Manganese and Chromium in Mixture, E50 Experiment 29 Spectrophotometric Determination of Manganese in Steel Using a 96 Well Plate Reader, E52 Experiment 30 Ultraviolet Spectrophotometric Determination of Aspirin, Phenacetin, and Caffeine in APC Tablets Using Solvent Extraction, E54 Experiment 31 Infrared Determination of a Mixture of Xylene Isomers, E56 Experiment 32 Fluorometric Determination of Riboflavin (Vitamin B2), E57 Atomic Spectrometry Measurements Experiment 33 Determination of Calcium by Atomic Absorption Spectrophotometry, E57 Experiment 34 Flame Emission Spectrometric Determination of Sodium, E60 Solid-Phase Extraction and Chromatography Experiment 35 Solid-Phase Extraction with Preconcentration, Elution, and Spectrophotometric Analysis, E61 Experiment 36 Thin-Layer Chromatography Separation of Amino Acids, E67 Experiment 37 Gas Chromatographic Analysis of a Tertiary Mixture, E69 Experiment 38 Qualitative and Quantitative Analysis of Fruit Juices for Vitamin C Using High-Performance Liquid Chromatography, E70 Experiment 39 Analysis of Analgesics Using High-Performance Liquid Chromatography, E71 Mass Spectrometry Experiment 40 Capillary Gas Chromatography-Mass Spectrometry, E72 Kinetic Analysis Experiment 41 Enzymatic Determination of Glucose in Blood, E74 Flow Injection Analysis Experiment 42 Characterization of Physical Parameters of a Flow Injection Analysis System, E76 Experiment 43 Single-Line FIA: Spectrophotometric Determination of Chloride, E79 Experiment 44 Three-Line FIA: Spectrophotometric Determination of Phosphate, E80 Team Experiments Experiment 45 Method Validation and Quality Control Study, E82 Experiment 46 Proficiency Testing: Determination of z Values of Class Experiments, E84 Index 815

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